DE1520221A1 - Graft copolymers and processes for their production - Google Patents

Description

DR. E WIEGAND DIPL-JNG. W. NIEAAANN DR. M. KOHLEB DIPUNG. C. GERNHARDT

M0NCH8N HAMIURO

Eooo monks 15, November 13, 1968

TIlIORAMMi, KAIfATINT. ... WALNUT STRASi11 «

W. 10 327/60 13 / Loe P 15 20 .221.8

Monsanto Company St, Louis, Missouri (V, St .A.)

Graft copolymers and processes. their manufacture.

Addition to the patent ............. (patent application P 14 2o 576.6)

The invention relates to graft copolymers obtained by polymerizing a monomer mixture, ^ consisting of styrene and acrylonitrile in an aqueous · Dispersion of a strongly crosslinked rubber-like compound J polymer are produced from butadiene and styrene, as well as a process for their production.

Graft copolymers by. Polymerize the mixtures of styrene and acrylonitrile monomers in aqueous dispersions of rubber-like diene polymers, including certain butadiene-styrene copolymers

90981670630 New

are known. The known graft copolymers of these types suffer from two known shortcomings. The first of these shortcomings is that the Graft copolymers are translucent to cloudy, while in many applications transparent polymers are required, such as packaging material. The second shortcoming of the known graft copolymers consists in that the surfaces of the objects made from it, often both matte and are rough, while in most cases it is desirable that the articles produced be smooth and shiny Have surfaces. ·

It has been found that certain styrene-acrylonitrile / butadiene-styrene mixed graft polymers, which are manufactured according to the special process according to the main patent are transparent and have smooth and shiny surfaces have if they work according to normal, for example processed according to the injection molding procedure. These Graft copolymers are produced in that j one is a mixture of styrene and acrylonitrile monomers

i ■. ·

(in an amount of 40 to 95% of the resulting graft

[mlachpolymerls iii ^^ lnag-wä ^ gien ipee-ien Share a high. crosslinked butadiene / styrene copolymer polymerized ..

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ORlGiNAL INSPECTED

- 5 - '■■' ■ '.' ■ '

It has now been found that improved graft copolymers made from the same styrene / acrylonitrile monomer mixtures and butadlene / styrene copolymers can be. The new graft copolymers not only have superior optical properties, i. Clarity, surface properties, but also superior physical properties, especially excellent Impact strength. «,

The substantial improvement in the properties of the graft copolymer compositions according to the invention is achieved by using a smaller amount, namely 2o to 60 parts, instead of 67 to 1900 parts of the styrene / Acrylonitrile monomers in 100 parts of the butadiene / styrene substrate polymerized "

According to the invention, a graft copolymer created, which is characterized, that it polymerize from a superstrate of 2ο to 60 parts of a Styrene / acrylonitrile monomer mixture to 10 parts of a There is butadiene / styrene copolymer substrate, the styrene / acrylonitrile monomer mixture polymerized in the superstrate consists of 60 to 9o wt. 9Ö styrene and accordingly 4o to 1o wt. 96 acrylonitrile, the butadiene / Styrene copolymer substrate a copolymer of a

. 909 816/063

Monomer mixture of 25 to 6o wt -.% Of styrene, up to 1.5 wt -.% Of a crosslinking monomer which contains a plurality of non-conjugated terminal ethylenic groups is dun butadiene as the remainder, and wherein, this butadiene / styrene copolymer a swelling index in benzene not above about 25.

The exact meaning and the Arbeltswelse for the determination of the Source Index are described below.

».- ■■■
The process for the production of graft mixed poly-

merizaten according to the invention by polymerizing a Monomer mixture of styrene and acrylonitrile in one

Butadiene / styrene polymer latex according to patent.,

(Patent application P 14 20 576.6) is characterized by that he

(1) 100 parts of a monomer mixture of 25 to 6o wt -.% Of styrene, up to 1.5 wt .-% of a plurality of non-kanjugierten, terminal Äthylengrüppen corresponds ^ keeps forming cross-linking monomer and butadiene as the remainder by at least 100 parts of water , which contains 2 to 4 parts of an emulsifying agent for the monomers mentioned and a catalytic amount of a free radical-generating polymer initiator, fnaaulgiert,.

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(2) at least 90% by weight of these emulsified monomers are polymerized in such a way that the butadiene / styrene copolymer which results in calibration has a swelling index in benzene of no more than about 25.

(3) a monomer mixture of 6o to 90 wt .-% styrene and correspondingly 4o to 10 wt .-% acrylonitrile aqueous dispersion of butadiene produced in stage 2 / Styrene copolymer in an amount from 20 to 60 Parts of the Mondmeren mixture per 1Q0 parts of the butadiene / Styrene copolymer incorporated and

(4) the styrene / acrylonitrile monomer mixture added in this way polymerized.

The graft copolymers are preferably according to of the invention by polymerizing a mixture of monomers from 65 to 80 wt .- $ styrene and correspondingly 35 to 20 wt .-? Acrylonitrile in an aqueous dispersion of the highly crosslinked rubber-like copolymer made of butadiene and styrene.

The two parameters that the butadiene / styrene copolymer characterize ·, which is used for the production of the graft copolymers, are:

1). the swelling index of the copolymer (which characterizes its degree of mitigation) and

2) the proportions of butadiene and styrene contained in the copolymer are included.

909 8 16./06 30

The butadiene / styrene copolymers used should have a higher degree of crosslinking than the usual butadiene / styrene copolymers, which are technically available. The degree of networking is quantitatively determined by the swelling index of the copolymer measured in benzene as by the test procedure described below is determined. According to the invention, the butadiene / styrene copolymer should have a swelling index of no greater than about 25, and preferably no greater than about 15.

When a maximum optical clarity and a minimum required for fogging in the graft copolymer the butadiene / styrene copolymer used for production should be 45 to 60% by weight of styrene and contain the remainder of butadiene or a mixture of butadiene and a crosslinking monomer. As set forth in various examples below., the inclusion of small amounts of a crosslinking agent reduces Monomers in the butadiene / styrene copolymers whose swelling index and improves the optical clarity of the graft copolymers produced therefrom. Additionally the inclusion of a crosslinking monomer in the Butadiene / styrene mixed polymer the surface properties of objects resulting from the

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mm ¹ T tm '

Graft mixed polymerizates are produced. This desired effect is partially offset by the fact that the inclusion of a crosslinking monomer in the butadiene / styrene copolymer substrate ^; adversely affects the impact strength of the resulting mixed graft polymer. This effect is particularly noticeable in mixtures of the graft copolymers with styrene / acrylonitrile copolymers. Accordingly, the maximum amount of crosslinking monomer that is included in the butadiene / styrene copolymer should not exceed 1.5% by weight or preferably 1.0% by weight. The caustic monomer is preferably incorporated into the butadiene / styrene oil copolymer in an amount of from 0.2 to 0.9% by weight. Suitable Vernetzüngsmonomere for incorporation in the butadiene / styrene copolymers include: Dinvinylbenzbl, allyl acrylate, allyl methacrylate, diallyl fumarate Diallylmaleaftf, diallyl adipate, "Diallyaphthalat and diacrylate and Dirnethacrylatester of polyhydric alcohols such as ethylene glycol diacrylate esters of λ.

The. aqueous dispersions of the butadiene / styrene-mixed polymers are used for preparing the graft copolymers., more usually under application can werdei prepared emulsion polymerization mixture regulations ^, Solbhe i> olymerisÄtionen However are carried out under conditions which ensure that Jia butadiene / ^%

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- θ -

Styrene mixed polymer is sufficiently highly crosslinked to have the desired .Qellindex. In general, the butadiene / styrene copolymers are crosslinked by introducing a small amount of a crosslinking monomer into the butadiene / styrene monomer mixture or by polymerizing or through the butadiene / styrene monomer mixture to a conversion of more than 90% both measures. , _Λ

Generally there will be 100 parts of the butadiene / styrene monomer mixture in at least 100 parts (preferably 15o up to 300 parts) of water with the help of micelle-forming structures Emulsifying agents, which are usually compounds, the hydrocarbon groups of 8 to 22 carbon atoms to highly polar soluble groups such as alkali and ammonium carboxylate groups, sulfate half-ester groups, sulfonate groups Partial phosphate ester groups or the like, contain bound. Examples of emulsifiers are: sodium oleate, Sodium stearate, the sodium salts of suIfaftialbestern of Fatty alcohols, which are produced by reducing the fatty acids of natural oils such as coconut oil, sodium abietate, Sodium salts and suIf © succinic acid esters, such as sodium dioctyl sulfosuccinate, Sodium salts of alkylated benzene and naphthalenesulfonates, like sodium dodecylbenzosulfonöt »sodium -

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salts of monosulfated fatty acid monoglycerides or the like. Such emulsifiers are usually used in a ratio of about 2 to 15 and preferably 2 to 4 parts per 100 parts of the monomers. The physical and optical properties of the graft copolymers and mixtures thereof with styrene / acrylonitrile copolymers are increased by using the minimum possible amount of the emulsifier to produce the butadiene / styrene copolymer. The polymerization medium can be a suitable, water-soluble, free radical-generating polymerization initiator, such as hydrogen peroxide, potassium or sodium persulfates, perborates, peracetai ^ percarbonates or the like. contain »where the polymerization initiators with activating systems, such as. Redox systems, including metals of varying valency and mild reducing agents, can be connected. In general, the polymer contains! Onsmedium also a chain transfer agent, such as a higher alkyl mercaptan of the type of dodecyl meroaptan, which both moderates the molecular weight of the butadiene / styrene copolymers and supports the initiation of the effect of the polymerization initiator in the polymerization. These polymerizations may at temperatures of about 4o to 8o ° p or in the case of activated systems including up to 80 ⁰ C in a range of low temperatures wieO ° auegeführt wtrdtn "

■ 1-09810 / 0630

- 1ο -

The graft copolymers are polymerized

Ren of preferably 40 to 60 parts of the styrene / acrylonitrile monomer mixture in an aqueous dispersion of 100 parts of the butadene / styrene copolymer manufactured. In the preparation of the graft copolymers, the mixture of styrene and acrylonitrile monomers is used to form the aqueous dispersion of the butadiene / styrene copolymer given and the resulting mixture is stirred and

W heated to a temperature of, for example, 40 to 100 ° C., at which the polymerization initiator present in the system / initiates the polymerization of the added monomers. If desired, fresh polymerization initiator can be added to the polymerization system with the styrene / acrylonitrile monomer mixture. In most cases, the remaining polymerization initiator used in the polymerization of the butadiene / styrene copolymer and / or the residues that are present in the rubber-like polymer chains * is sufficient to initiate the polymerization of the added monomers. Preferably no emulsifiers are added to the polymerization system and when the polymerisation is carried out in this way, almost the total amount of the added S1; yrol / arylonitrile monomers is dispersed in the previously formed rubber-like polymeric parts and the effectiveness of the grafting

9Q9818 / 0630

reaction is very high.

The graft copolymers finally obtained can be obtained from the aqueous dispersions by customary means such as coagulation, freezing or drum drying The physical properties of the graft copolymers lie between rigid rubbers and hard resins.

The graft copolymers according to the invention can be used for the production of polymer mixtures with rigid% styrene / acrylonitrile copolymers containing 60 to 90 and preferably 65 to 80 wt -.% Styrene and correspondingly

4o to 1o and preferably 35 to 2o wt -.% Acrylonitrile are used. .

contain / The polymer mixtures can be obtained by mixing of latices and recovery of the polyols from the mixed ones Latices are made. If necessary, they can by simply mixing together a mixture of the solid polymers at an elevated temperature for a period of time sufficient to achieve an intimate melt mixing of the to achieve both polymers. A . such mixing-can in rubber rollers, Banbury mixers, Screw extruders and other types of common processing systems for plastic materials. will lead «,.

0.9.816 / 06-3

The graft copolymers as such and mixtures of the graft polymers with styrene / acrylonitrile mixed polymers can be used to produce high strength injection molded articles, to produce extruded sheets or webs and films and for the production of other very resistant objects according to known methods Working methods are used.

If desired, stabilizers, antioxidants ^ agents, plasticizers, lubricants, dyes and others Usual additives to the graft copolymers and their Mixtures with styrene and acrylonitrile copolymer & n be incorporated ι. ·

The term "graft copolymer ¹¹ used here refers to the copolymer which is produced by polymerizing the styrene / acrylonitrile / acrylonomer mixture in an aqueous dispersion of the butadiene / styrene copolymer. The butadiene / styrene copolymer is called the •• substrate" and the styrene / acrylonitrile polymerized mono- w merenmiechung referred to as the "superstrate. ¹¹

The invention is illustrated below by way of examples explained in more detail. All parts denote weight parts.

Example 1 *

A butadiene / styrene copolymer latex is under Made using the following polymerization approach.

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- Kownonontfr '. ·. <■. ., ICoilo

V / aooor ';.' ■ < V 200

Butadiene '' ■ '(' ■. 50

Styrene,. /.-■ '' \ ';"·■;:/;' .-. '50. Divinylbonaol · .- "·. % 0.75

^-,: ■■■■ ·; ■ '■■ ■': '; 5:.

Dodooylmeroaptan ν \ ö »3

i Waooor and soap have been in a druokfoöton »with Agitator installed in an autoclave.

remove / And then chilled under Stioketoff. Uo been

Then the remaining components "of the polymorlsation oyotem augeßebon and the autoclave closed" The polymerisation is carried out! by obtaining the heating for 43 hours on SO ⁰ O. The conversion of the clay solids to polymer loat is SQ S ^ * ...

A sample of the butadiene / styrene misoh polymer. . . is obtained from the latex and has a swelling index (in Bonaol) from woniger ale 25 »as by dio below bo-. wrote · Ve ** uohoarboit9woiee determined 'throws · .. -'

> The term "Quoliindex" is used here in the sense of »wants to enter into full subscription« on page 33d in "Synth« tio Subbtfr * from 0 · S «Whitby» John Wiley A Sons Xno · »

New York City, 1954. Specifically, the swell index of a rubber as the ratio of the weight of the solvent-swollen gel (the gel is the rubber portion that is insoluble in the solvent) to the weight of the dry gel defined · To determine the value of the The swelling index is 0.3 g of the butadiene / styrene polymer melt placed in 75 ml of benzene and kept at 20 ° C in complete darkness for 24 hours. The resulting mixture is then passed through a tared stainless steel screen (corresponding to a clear mesh size of about 0.150 mm) filtered and the weight of the insoluble polymer swollen by the solvent is determined after the insoluble polymer is washed in 10 ml of benzene. Cine

• w

Part of the filtrate is evaporated to dryness, to determine the weight of the butadiene / styrene copolymer which is soluble in the benzene. The source index is then calculated according to the equation below calculates. _vori

Weight / polymer swollen by solvent (g) Source index =

o _t 3 weight of benzene-soluble polymer (g)

To that, as described above '! butadlene / styrene Mlachpolymerisatlatex produced are 22 parts of water, 5o parts of a monomer smell containing 72 wt .- # styrene and 20 Gev «- # contains acrylonitrile and potassium perulfate in the amount

909018/0630

of o _f 2 weight-96 given to the monomer mixture. The Eteiktlohsmischung is heated to 70 ⁰ C until the total amount of the styrene monomer is polymerized acrylonitrile /. The graft copolymer emulsion is cooled to room temperature under a nitrogen atmosphere, and a portion of a styrenated phenol antioxidant is added. The graft copolymer obtained is obtained by drum drying.

6 polymer mixtures are obtained by mixing the styrene / acrylonitrile graft copolymer obtained above with a copolymer of 72% by weight of styrene and 28% by weight of acrylonitrile, which has a specific viscosity of 0.07, as in a 0.1 # igen solution in dimethylformamide at 20 ° C was established. The proportions of the two polymers used are such that the polymer mixtures contain 1o, 15 »2o, 25» 30 and 35% by weight of the butadiene / styrene copolymer used as substrate in the graft copolymer. The λ physical properties of the polymer mixtures are given in Table I. The impact strength values were determined here and in the examples below using the ASTM method.

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Table I.

Weight .- $ of the BD-S (I) impact strength tensile at ^ elongation module ₍ mixed polymer at 2o ° C break «at χ '

in mixture ft.Ib./in
(2) kg / cm fracture kg / cm Io o, 5 457 11 0.29 15th 0.6 436 16 0.26 2o 1.1 401 22 ' 0.23 25th 2.4 373 30th 0.19 30th 4.2 337 41 0.16 35 7.2 309 39 ' 0.14

(1) BD-S

(2) 12.7

«Butadiene-styrene 12.7 mm rod, notched radius« 0.25 mm

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-17- j '* ·' ■

From the table above iot oroiohtlioh that the V / orto der Zugfootigkoit and dos Modulo dor Polymorlsatmisohungen fall, if the percentage dos butadion / styrene-Uisohpolymorioatoubotratoo dos Pfropfaisohpolymorisates, τ / olohoo in the Polyraorisataisohung is aooohlosson increases "in contrast" Wertο the impact strength and elongation at break En as soon as

the percentage of the butadiene ~ styrene * -misohpolymoreate substrate of the graftmisohpolymer included in the mixture is increased

", ·. · 33ο1ατ> 1ο1 2

A series of graft polymeric polymers were made by polymerizing 2, 40, 50, 60, 60, 100 or "150 parts of an monomeric mixture of 72 Qevr"? " Styrene and dew · i * aorylnitrile in an aqueous dispersion containing 100 ropes of the butadiene / styrene copolymers described in Example 1, produced identical described in Example 1, The graft polymer was obtained by means of Troßmöltrooknen

J «doe of the previous subscription to the drilling operations in dom is carried out with the drilling operation in example 1

^{/ V> :} ' ^] '"^:> ■. ':"·',"'' 5 ^Τ; Ί>V;■■■; ■■ .. ■ '' - ^ ^.: V · ■ ■■■ < ■. '·. Badpriginal

·; Λ

benen copolymer of 72 wt .- # styrene and 28 wt .- % acrylonitrile mixed in such proportions that the butadiene / styrene copolymer substrate of the graft copolymer represents 30 % of the polymer mixture. A polymer mixture for comparison purposes, by mixing 3o parts of the butadiene / styrene Mischpolyraerisats used as the substrate in the graft copolymer with 70 parts of the copolymer of 72 parts by weight of styrene and 28 wt 9i - manufactured% acrylonitrile..

The physical properties of the resulting polymer blends are given in Table XI.

Table II

Parts S-AN (I) impact-resistant tensile at break % elongation modules

Monomeric speed at 2o C kg / cm at break x1o "«

grafts at ft.lbs./inch kg / cm

BD-S (2) (3) - - ■ '

Substrate

o, 4
3.3.
7.0
4.2

3.1
2.4
1.7
1.0

337 330 337-337 337 337 366 394

51

43

41

38

34

30th

28

o, 18:

o, 17 o, 17 o, 16

o, 17 o, 16 o, 16 0.17

S-AN = styrene-acrylonitrile BD-S = butadiene-styrene.

12.7 x 12.7 mm rod, notch radius

o, 25 mm

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Ea zeißt oioh that dio SohlaßaühiGlcoit dor polynoron ilicohungon in boaohtliohor Yteiao is influenced by dio Llongo dor styrene-acrylonitrile ilononoronaieohung "dio dos butadione-StyrolliioohpolyweriflataubBtrat doo Piropfaiflohpolyaoriaata grafted v / Urdo _t · Inoboaondoro achieved dio impact strength dor Mieohungoa Cinon Maxiwalwort when etv / 40 ropes of styrene-acrylonitrile-monomorozimiuchuns on the butadione-styrene-Mioohpolynorieatoulaatrat auf ^ opfrop ^ t

and sinks roughly "when 'dio men ^ o dor so grafted styrene-aorylnitrile-monomoron mixture ontwodci- ab- odor sunizamt · Ee can still be boooaohtot that the Bruohdohnunß decreases, although the "severity of the styrene-aorylnitrile-HonoBorenciieoliung, the butadionotyrolnioohpolyciorioatsubstrat is grafted from the butadionotyrolnioohpolyciorioatsubstrat" rises.

Ea is a Hoiho of butadiene-styrene- ^ iQohpolymori · saton duroh Polymorioioren of luonomoronmtßahunGün, the 50 toilo butadiene » % 0 ropes of styrene and 0.25» 0.75 * 1 »O» 1 _t 2 $ or * 1 » 5 ropes of Bivinylboneol contain »set up * Kit The exception of the Zueenmoneet & ung the lionomoronbeochiakung is the applied PolymerieationcarboitQw ^ ieo nit the idontieoh · shown in Example 1. .

A series of sfropft & ieohpolynerieaten is duroh Polymerization of 40 ropes of a Uonomoronuiaohung »dio

9098 16 / 063Ö, "-" ^J X '. >. 'S

/ ·. ; ..:; V: BAD ORIGINAL

■ \

i - 2o -

72 Gow. i » Styrene and 20 Cow · yS Aorylnitril cnthUlt, in wiifiri ^ on Dioporoionon, the 100 Coile iodco dor iia voratohondon Aboohnitt horgootollton Butüdion-Styrene-MioohpolyiaQrioatö contains on, boroltot. Dio applied Pii'opfmieohpoiyiaorieationaarbeitaweioo lot different coito with dor in Boispiol 1 boaohriolionon idontiooh «£ in Toil oinoo atyroniorton Phonol-AatioxydationaaittolG jodeia dor Laticoo oinvorlies and the P ^ ropfioohpolyiaonnrocknen Duro-spray-drying. .

Jodoο the vorotohond hergoatollton Pfropiaiochpolynorioatc is used with dom in example 1 toechriGbonon Miachpo-

■ ", ·· ■■ lyaoriöat auo 72 ßew · # styrene and 28 wt. # Aorylnitrile in ßolohon proportions tJGmisoht that the butadione-styrene-Vaioohpolysiorisatoubatrat dos Pfropfoiisohpolysiorioata 50 Gqvv» f & dobonden ßiohiohio dobondor ßiohioh let in laboll © 111 Aufgo-

! Pabollo II: at 20 ^ σ Ropes
BD {2)
JBD-S f DVB (I) / i00 ropes. '
and S (3) in ' 10 .1 ■■; ■ ■ ■ ■■ · ■ Ο ■ .. ";. ·. _ ■■ _ ^J. ■■■■ - ■;.: ■ .- ■ '. 10
5 "1 \ : ^0.25,: '. · '\ -; ί: ^{V V:} V ·.
0.75 2 »9 1.0. 0 . II % ** w

• ORIGINAL BATHROOM

(1) DVB «. Divinyl Lidnzol

(2) BP m butadiene

(3) S »styrene

(4) -12.7x12.7mm istat), Xorben-Radiua β ο, 25 mm

Y / io "au ^ ~ de1FWretohendon table is eroiohtlich, UIq bottom viscosity dor Mioohunson drops rapidly when the amount of divinylbonsol which is in the butadione-styrolilio.ohpolymerloatsubstrat des graftttaioohpolymoricato oinßO £ 30hloDsea rises r ^ vird λ effect is teilwoiee canceled by "the clarity lind Oboriläohoaoißonschaitea (d" h · Glana and Qlutto) of be ßpritsaußatüoko verteosort "aofe & ld dio JAoxiqq on Divinylbonsol _t is in the butadiene-styrene Mioohpolyzaeridat cinßosohloösen iot increased"" ■

Example 4 '.

A latox of a EutacLion-styrene-MiDchpolymerioate, the 50 ropes of butadione, 50 ropes of styrene and 0.75 Dlvinylbcn-20l contains § is manufactured according to the work described in Example 1 "three additional latices of the same sutadiene-styrene -Hißohpolymerisateo been qqzuIQ an identical Arbeitovreiee "manufactured with Uqv except Dab, 5 ropes of Uatrluastearat-Esiulgieraittels through 3, BAW. 15 ropes Hatriuiaotoarat are emotet · Four sfropimitehpolyinerieate advertise through Polymeric

. : _v ; 909816! / 063Q ₁ "''.! ' ^ ₀ ORIGINAL

. "', oioron of 40 parts oinor ttonoaoronaioohunc, dio aua 72 _:. '. \ Oow. fi Stjwol and 20 Gow« $ aorylnitril bootoht, in oinor '· wüßrigon Bioporoion, dio 100 parts iodes dor in voroto- \' hondon Absohnitt horgootollton butadione-styrene-I'isohpoly «· '■":';'contains morisato, manufactured; Sio vorwoiidote graft mix «»: - \ polymorisationsarbeitswoiso, on the other hand, is Qit of the in

'Example 1 described identically «Part of oines styro ·».' · '. · Nated phenol antioxidant is introduced in ^ edos of the Ia-:. ■? ·. ■ tic ο s and the graft copolymers are.:;. "· .., obtained by spray-drying · '=';.';.. iodine the hergosteilten in vorhorstohcnden section, ^ν';;: · Pfropfiaioohpolymorisato v / ill with dom copolymer of ': ■: ·' i 72. Gcw ·. $ styrene and 2Q Gow "$ Aorylnitril that eat example · :: _··· 'Ί bcBchrieben is" in such proportions: mixed "that there © veins!' ^ butadiene tStyrol-Mischpolymorisatsubstrat dos .Pfropfmisch ·" ■ ■ . 'Polymer 30 wt. F * of the resultant I & l & ohungen. • -: forms «bio-physical properties of this mixture»! · '· "' ·· '"gen' are listed in gabelle 'ZV " i.''* ^ -''----'''';' - '' ^ ''''' ^! ' ■ '■' ■ «' " · ■. .- '■ ·'. ■ '' ■ - '.. ·; Tabel

Sharing emulgienjiit- impact resistance. ■ '9a expansion' modulus j-

tels that are used to produce. at.? o ° C v "-. B ^ chp J * at. χ 1ο""«

lung, of the plug with m- ft.lbs./ip. ·· -Ifg / cmf: '1. Break kg / cm

pol3nnerisats use; - '(I) X''' ^: ·. ·. ···· '. ·. . · ■ ·. '"'';.;·' ·. ·. (1) det are · '■''. ·. ·'". ··· ·· '"■' - '' -

· ·· ■ ··. "■ · '· ■ ·' ■ / ■ ·· '4,6 ·' .. ■ '../.323 - ·" 5 ^'. 'O, 16

· · · '2.7 ■■■■■ "309 .. 5o" o, 15.

(D'12,7, χ-1.2 ·, .7 '

mm rod, Zern radius = 0.25 mm!

•• 1 ■ ·, .. V., 90'98t670B3.0 ^: ''. ^ ^;

COPY

Eo-lot au boiaörkon that dio Sohloßaänißkoit dor Uioohun ^ on I) GaOlItIiCh is increased as soon as'dio Uonßo an emulsifier »dao sur production deo Butudion-Styrol-Kicohr ·. polymorioatsubfltrato doa Hropfmiochpolymoriürats vcrwondot v / ill is reduced dor "Ue wird'eine geringo Zunaiiae and a flume Abntiiitao dor Bruchdehnun2 .Once the Monas οά Emul ^ ionaittol vorringort is!" The clarity dor Misohungon v / ill also pre- ■ beosert "as soon as the amount of building agent is reduced

BoiBpiel, .5

Sin graft flea polyaioriöai; y / ird duroh Polynoriaierea of 50 ropes of a Mononerenmiacliung, the Ö5 Gow. ? S styrene and .15 wt. # Acrylonitrile contains, in a wäßri ^ cä

Dispersion, the 100 ropes of deodorant in example 1 boschriobonon Contains butadiene-styrene-HioohpolymorinatD, hor ^ estollt. With Auflnahao the addition of the Verwondoton styrene-aorylnitril-Hononerennieohuns is the PolymeriGationaarbeitswoise » those for the production of the ^ iropinisohpolymerieate is used, identical to that used in Example 1, 2> aa Pfropfaiöohpolyiaorisat is duroh! Eronmoltrooknen won · · ·

- Daa in the above subscription no grafting

9098t67Q'63U. . "■ * ■

COPY

• '"' ■ BATH

^: - 24 -

Misohpolyraoriaat is nit a MlDohpolymoricat of 05 Gew · i » styrene and 15 Co? /» # Acrylonitril with olner oposifioohon Viokosität of about O ₉ East bostlcat in oinor 0.1 # solution In Diraothylfornaald at 2O ⁰ O, in solohon proportions consumed » that the Butudien-ßyrol-MioohpolynoriBatsubetrat des Graft Misohpolyaerieat 30 Oew. i » the poIymerizatmieohung shows» bio orgebtnde Polyaorleatmiochunß eats durohigh -and has a permeability of more than 4 ft · Ibe./inoh up to 20 ⁰ O. -

Sell A is repeated with the exception that the ßyrene-acrylonitrile-liiDohpolyraorieat, wolchoa with dom PfropftoiBohpolyaerieat is comicoht ,. _fc dae in Example 1 is beoohriebone Btyrol-Aorylnitril-MiooUpolymorioat. Comparable results have been obtained · V

' BelBplel 6 :.

. Sin Pfropfaleohpolycierisat is obtained by polymerizing a SO ropes Mönomerenniaohunß containing 60 wt. I * of styrene and 40 OEW · i _»t of acrylonitrile in a wäßrlgen Dicpereion 100 doo ropes in Example 1 boeohrio-

benen butadiene-styrene-Mioohpolynerioata manufactured · Wit Exception »dor SSusaomenseteunc dor vonrondoten Btyrol-Aoryl-

let mr hear tllunß do graft

ORIGINAL

•; ■■ '

. aioohpolymericatu appliedto Polymoriaationaarboitowoiöe ■ with dor in example 1 bouohriobonon idontiooh. Dao Pi'ropf-,

'.'-. · Copolymer is duroh · Sromnoltrooknon gowonnon.

'■> v Dao ia preceding Aboohnitt bosohriobono graft ...

;, -. '', mieohpolymeriaat; becomes with a Mioolipolyiaöriaat from 60. '-'-. ".- / ·' · '■' ■ ·. ■■.

.: ■> ,; · ■ Ggw. £ styrene and 40 wt. $ · Acrylonitrile »v / elohoo an epe zifiGohe ViakositUt of about 0.07 »boetiwat in cinor 0 ₉ 1 £ i & on Löcuns in Dimothyliorpanid boi ₍ ? 0 CJ _P in d oils hon Antoilen ßömißoht, because the butadione-styrene-UiDciipolynorieatsubstrat des Pfropiaicühpolym- /. .; aerieataisohung auamaoht · The resulting polymerisat- ■; misöhung is durohoiohtig and has a bottom viscosity

voa achr as 4 ft. lbe »/ inoh bai

Λν '^; : ···· ·: '■ ■ ·', Vv- ¹ M ^ Nv. ' ■■■■ '''■''' · '' - ■ '. '' ■■ "'■' ■: ', ■■■■>■' * '· ■' ■■ '. ^! "·'. · -. '

- · ν

bad original:

.Vi ¹ '.

Claims (6)

Claims. - ~ 1) Graft copolymer, characterized in that that it consists of a superstrate of 20 to 60 parts of a polymerized styrene / acrylonitrile monomer mixture to 100 parts of a butadiene / styrene copolymer substrate consists, the polymerized in the superstrate Styrene / acrylonitrile monomer mixture of 6o to 90 wt .-% styrene and accordingly 4o to The butadiene / styrene copolymer substrate consists of 10% by weight of acrylonitrile a copolymer of a monomer mixture of 25 to 60 wt .-% styrene, up to 1.5% by weight of a "crosslinking monomer which has a plurality γόη contains non-conjugated, terminal ethylene groups and butadiene as the remainder, and this butadiene / ijstyrene copolymer has a swelling index in benzene of does not have above about 25. 2) graft copolymer according to claim 1, characterized in that the butadiene / styrene copolymer substrate is a copolymer of a monomer mixture of 25 to βο wt .-% styrene, ο, 2 to o, 9 wt .-% of a plurality of non-conjugated, . Terminal ethylene groups containing crosslinking monomers and butadiene as the remainder. 3) graft copolymer according to claim 1, characterized in that the butadiene / styrene copolymer substrate is a copolymer of a monomer mixture of 45 to 60 wt .-% styrene, up to 1.5 wt .-% and in particular -9.2 to 0.9 96% by weight is a crosslinking monoijieren containing a plurality of non-conjugated terminal ethylene groups and the remainder is butadiene. 4) Graft copolymer according to one of the claims to 3 »characterized in that the in the superstrate polymerized styrene / acrylonitrile monomer mixture of $ 5 to 8o wt .- # styrene and correspondingly 35 to 20 wt .- J6 Consists of acrylonitrile. / 5) , a process for the preparation of graft copolymers by polymerizing a monomer mixture of styrene and acrylonitrile in a butadiene / styrene polymer latex according to patent ....... (patent application 3P 14 20 576.6), characterized in that one (1) 100 parts of a monomer mixture of 25 to 6o wt .-? 6 styrene, up to 1, 5 wt .- # one a plurality f of non-conjugated, terminal ethylene groups containing crosslinking monomers and butadiene as the remainder in at least 100 parts of water, the 2 to 4 parts of an emulsifying agent for said monomers and one catalytic amount of a free radical generating polymerization initiator contains, emulsifies, 9 0 9816/0630 ORIGINAL INSPECTED (2) at least 90 wt -.% Of these emulsified monomers polymerized so that the resulting butadiene / styrene copolymer no longer has a swelling index in benzene of than about 25, (3) a monomer mixture of 6o to 9o wt -.% Styrene polymers · rol and 4o according to 1o 96 parts by weight of acrylonitrile the aqueous dispersion prepared in aufe 2 of the butadiene / styrene Mischpolymerlsats in an amount of from 2o to 6o parts of the monomer mixture each Ίοο parts “of the butadiene / styrene copolymer incorporated and (4) the styrene / acrylonitrile monomer mixture added in this way polymerized. 6) Method according to claim 5 »characterized in that a monomer mixture is emulsified, the o, 2 to o, 9 - Contains wt .-% of the crosslinking monomer. ⁹ ° 9816 / O63O ORiGiNAL / NSPECTED